CN115894911A - Epoxy modified hyperbranched polyamide-amine high molecular polymer, preparation method and application - Google Patents
Epoxy modified hyperbranched polyamide-amine high molecular polymer, preparation method and application Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 35
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- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 5
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- 239000007787 solid Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
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- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 3
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 3
- 229920000297 Rayon Polymers 0.000 claims description 3
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- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Polyamides (AREA)
Abstract
The invention discloses an epoxy modified hyperbranched polyamide-amine high molecular polymer, a preparation method and application thereof, and belongs to the technical field of high molecular materials. The raw materials comprise, by mass, 86 parts of methyl acrylate, 63-175 parts of diamine, 3-26 parts of dicyanodiamine and 1.5-26 parts of epichlorohydrin. The hyperbranched polyamide-amine is prepared by taking methyl acrylate and diamine as main raw materials through Michael addition reaction and amidation reaction, then grafting amino and imino on a branched chain of the hyperbranched polyamide-amine through dicyanodiamine and epoxy chloropropane, and introducing a reactive group epoxy group. The high molecular polymer prepared by the invention can effectively reduce the use amount of inorganic salt and inorganic alkali in the dyeing process of the cellulose fiber fabric, improve the dye uptake and the fixation rate of the reactive dye, and reduce the influence on the color light of the dyed fabric after modification treatment.
Description
Technical Field
The invention relates to an epoxy modified hyperbranched polyamide-amine high molecular polymer, a preparation method and application thereof, belonging to the technical field of textile auxiliaries.
Background
The cellulose fiber mainly made of cotton fiber has the advantages of comfortable wearing, biodegradability and the like, is popular with people, and occupies a large share of the fabric market. The reactive dye is the most common dye for dyeing cellulose fibers such as pure cotton fabrics and the like, and has the advantages of bright color, complete color spectrum and excellent wet treatment fastness. However, because the cotton fiber dye liquor is electronegative, the adsorption of anionic dyes such as reactive dyes and direct dyes in the dyeing process is very weak, so that the dye uptake and the fixation rate are low. In order to improve the dye-uptake and the fixation rate of the reactive dye, a large amount of inorganic salt, such as sodium chloride or sodium sulfate, must be added in the traditional dyeing process to improve the dye-uptake of the dye. The salt content is different according to different dye structures and colors, and generally 30 to 150g/L is needed. And in the later dyeing stage, inorganic alkali is required to be added so as to further improve the dye uptake and the fixation rate. Inorganic salt used in the dyeing process cannot be degraded and is difficult to recover, so that wastewater with high salt content and high chroma is generated in the dyeing process, the cost of dyeing materials for dyeing processing is increased, the defects that the wastewater is difficult to treat and the treatment cost is high are caused, the environment is polluted, the negative influence on water quality and soil is great, and the ecological green development of textile printing and dyeing enterprises is severely restricted.
In recent years, with the increase of the requirement for environmental protection and the increase of the cost of dyes, the improvement of the utilization rate of reactive dyes has received extensive attention in the field. The existing fiber cation modification technology, wet short steaming dyeing technology and less-water and non-water dyeing technology show the effects of improving the utilization rate of dye and reducing the use amount of inorganic salt during pilot plant test or special variety processing, but the corresponding process practicability, stability and processing cost still limit the application and popularization of the fiber cation modification technology, the wet short steaming dyeing technology and the less-water and non-water dyeing technology. Foam dyeing, dye liquor spraying and vacuum dehydration technologies based on low liquor carrying rate dyeing also show higher application scenes, but the requirements on equipment are high, and the actual production brings higher economic pressure.
The demand of new reactive dye dyeing technology for reducing the difficulty of wastewater treatment is increasingly urgent while the utilization efficiency of dyes and chemicals is improved, the realization of clean production of cellulose fiber fabrics is a necessary direction for the development of textile printing and dyeing industry, and in order to realize low-salt (or salt-free) low-alkali dyeing of reactive dyes and effectively reduce the use amount of inorganic salt and alkali, extensive research is carried out at home and abroad. Currently, the existing research is mainly focused on three aspects: 1. synthesizing a novel low-salt reactive dye; 2. carrying out cationic modification on cellulose fibers; 3. salt-free dyeing crosslinking agents are used. Among them, the low-salt reactive dyes have the problem of uneven color spectrum, the cation modified cellulose fibers have the problems of complex process, uneven dyeing and the like, and the salt-free dyeing crosslinking agents have the problems of different performances, color light change of dyed products and the like, so that the application of the salt-free dyeing crosslinking agents in actual production is limited.
Specifically, the cationic modification of the cellulose fiber is mainly to fix a cationic compound on the cellulose fiber through chemical combination or physical adsorption so as to improve the affinity between the dye and the fiber, thereby improving the easy dyeing rate and the fixation rate of the dye and realizing the reduction or even no use of inorganic salt in the dyeing process. At present, dendritic polymers are used in this aspect, and the dendritic polymers include hyperbranched polymers and dendrimers, and the molecular structures of the hyperbranched polymers and the dendrimers are schematically shown in fig. 1 and fig. 2. The dendrimer shown in the figure 2 is a novel polymer material, is a monodisperse polymer with a dendritic structure and high branching degree, has a regular and controllable branching structure and a definite molecular weight, only has branching units and terminal group units in molecules, and functional groups are all on the surface of the spherical macromolecule, so that the dendrimer has low polydispersity, controllable surface function and high reactivity. However, the material must be prepared by multi-step continuous synthesis, and after each step of synthesis, operations such as' protection-deprotection, separation, purification and the like are required, so that the process is very complicated. The difficulty of preparation leads to high price, limiting its application as consumable material.
The hyperbranched polymer shown in figure 1 is a macromolecule with a defective dendritic structure, the whole molecule is not completely symmetrical, so that the shape of a single molecule of the hyperbranched polymer is ellipsoidal, and the non-intra-chain winding performance of the hyperbranched polymer is determined by the multi-terminal group structure of the hyperbranched polymer, so that the hyperbranched polymer has the properties of high solubility, low viscosity, strong chemical reaction activity, good fluidity, easy film formation, easy functional modification and the like. The hyperbranched polymer is different from the traditional linear polymer, has a special three-dimensional structure and rich end groups, has high solubility, low viscosity and strong chemical reaction activity, has attracted the attention of researchers in recent years, and has application and research reports of a large number of hyperbranched polymers in the fields of paint, polymer blending modification, drug slow release, conductive materials, electroluminescent materials, nano material preparation and the like. In the prior art, low-generation polyamide-amine dendrimer is applied to cotton fabric by an SM Burkinshaw research group and domestic researchers slowly-thickening to improve the dyeing property of the cotton fabric, so that a satisfactory effect is obtained, but the polyamide-amine dendrimer has complex synthesis steps, extremely low gradual purification yield and high production cost, and cannot be widely applied in actual production.
Zhang Feng et al for realizing salt-free dyeing process of cotton fabric by using methyl acrylate and diethylenetriamine as raw materialsThe melt condensation polymerization method synthesizes water-soluble amino-terminated hyperbranched polymer and is used for modifying cotton fabric, the modified cotton fabric realizes salt-free dyeing, and the dyeing fastness of the modified cotton fabric (salt-free dyeing) is equivalent to that of the unmodified cotton fabric (dyeing under conventional conditions), but the method needs to add citric acid and sodium hypophosphite in the modification process, and firstly uses NaIO 4 The cotton fabric is slightly selectively oxidized and then reacted with a water-soluble amino-terminated hyperbranched polymer. Meanwhile, the colored light of the dyed fabric prepared by the low-salt or salt-free dyeing of the reactive dye after the fabric is modified by the scheme is greatly different from that of the unmodified cotton fabric (dyed under the conventional condition), and the color light deviation is not beneficial to the quality control of dyeing.
In addition, in the technology of modifying cellulose fibers by adopting hyperbranched polyamide-amine and applying the modified cellulose fibers to an active low-salt low-alkali dyeing process, amino groups and imino groups on hyperbranched polyamide-amine branched chains can only be covalently combined with hydroxyl groups and amide groups on amorphous areas of the cellulose fibers, and the color fastness performance of dyed fabrics cannot reach the color fastness of unmodified cotton fabrics dyed under the conventional conditions. The defects result in that the low-salt and low-alkali dyeing process and technology of the reactive dye cannot be popularized and applied.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an epoxy modified hyperbranched polyamide-amine high molecular polymer, a preparation method and application thereof.
The first aspect of the invention provides an epoxy modified hyperbranched polyamide-amine high molecular polymer, which comprises, by mass, 86 parts of methyl acrylate, 63-175 parts of diamine, 3-26 parts of dicyanodiamine and 1.5-26 parts of epichlorohydrin.
Further, the diamine includes at least one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, and hexylenediamine.
The second aspect of the present invention provides a method for preparing the epoxy modified hyperbranched polyamide-amine high molecular polymer, comprising the following steps:
s1, taking an organic solvent as a reaction medium, adding methyl acrylate into diamine, mixing at the temperature of 10-25 ℃, heating to 20-50 ℃ after mixing, reacting for 12-48 h, continuously heating to 120-150 ℃ in a gradient manner, and reacting for 2-4 h;
s2, adding dicyanodiamine into the reaction product of the S1, and reacting for 2-4 h at the temperature of 80-85 ℃;
and S3, reducing the temperature of the system to 0-15 ℃, adding epoxy chloropropane, mixing, heating to 15-50 ℃, and reacting for 0.5-2 h.
Further, the organic solvent is methanol.
Further, the temperature rise gradient of the gradient temperature rise is 10 ℃.
Further, the dicyanodiamine added in S2 is dicyanodiamine aqueous solution.
The third aspect of the invention provides the application of the epoxy modified hyperbranched polyamide-amine high molecular polymer in modified cellulose fiber fabrics and in a reactive dye low-salt and low-alkali dyeing process.
And further, padding or soaking the cellulose fiber fabric in working solution and then drying, wherein the working solution is prepared from the epoxy modified hyperbranched polyamide-amine high polymer product and water and has the concentration of 5-10 g/L.
Furthermore, the solid content of the epoxy modified hyperbranched polyamide-amine high molecular polymer is 20%.
Further, the drying temperature is 100-150 ℃.
Further, the cellulose fiber includes cotton fabric, viscose fabric and hemp fabric.
The invention has the beneficial effects that:
1) The surface of the epoxy modified hyperbranched polyamide-amine high molecular polymer has rich amino and imino, after the epoxy modified hyperbranched polyamide-amine high molecular polymer is used for modifying a cellulose fiber fabric, an active functional group epoxy group on a high molecular polymer branched chain is chemically bonded with part of high-activity primary hydroxyl on a cellulose fiber amorphous region macromolecule main chain, and rich amino and imino are introduced on a cellulose fiber macromolecule chain, so that a large number of dyeing seats are introduced for the cellulose fiber, the ion adsorption effect on anionic groups of active dye molecules is improved, the dyeing of dyes with negative charges is facilitated, the use amount of inorganic salts in the dyeing process is reduced, and low-salt even salt-free dyeing is realized.
2) The amino on the macromolecular branched chain of the epoxy modified hyperbranched polyamide-amine high molecular polymer belongs to organic alkali, has a catalytic action on the chemical bonding of the activity of reactive dye based on cellulose, is favorable for strengthening the color fixing reaction, and improves the dyeing rate and the color fixing rate of the reactive dye, thereby effectively reducing the using amount of inorganic alkali during dyeing and realizing low-salt or salt-free and low-alkali dyeing.
3) The hyperbranched polyamide-amine is prepared by taking diamine and methyl acrylate as raw materials, and modification of dicyanodiamine and epichlorohydrin is beneficial to controlling the amine content in a high molecular polymer and the branching degree of the polymer, effectively reduces the influence on the color light of dyed fabrics after modification treatment, improves various color fastness properties of the dyed fabrics, and is beneficial to improving the quality control of a dyeing process and a dyed product.
4) In the method for preparing the epoxy modified hyperbranched polyamide-amine high molecular polymer, an intermediate generated in the preparation process does not need to be purified, and the polymerization condition is far less strict than that of preparing the polyamide-amine dendrimer. The preparation method of the invention has simple and easily controlled process, easily obtains the polymer product with large molecular weight, has low viscosity of the polymer system and has practical popularization value.
5) The epoxy modified hyperbranched polyamide-amine high molecular polymer is applied to modification of cellulose fiber fabrics, so that the modified cellulose fibers can be used for an ecological dyeing process with low salt and low alkali of reactive dyes, the content of inorganic salt in printing and dyeing sewage is effectively reduced, the environmental pollution is reduced, and the epoxy modified hyperbranched polyamide-amine high molecular polymer has excellent social benefit and economic benefit. The modification process is simple, alkali and acid washing are not needed, the fabric is not damaged, and the soaping color fastness and the dry and wet friction color fastness of the modified and dyed fabric are equivalent to those of the conventional dyeing process.
Drawings
FIG. 1 is a schematic diagram of the molecular structure of a hyperbranched polymer in the prior art, wherein A and B are reactive groups.
FIG. 2 is a schematic diagram of the molecular structure of a dendrimer in the prior art.
FIG. 3 is a reaction equation for synthesizing the hyperbranched polyamidoamine high molecular polymer (hexamethylenediamine is used as the raw material) of the present invention.
FIG. 4 is a schematic structural diagram of the epoxy-modified hyperbranched polyamidoamine high molecular polymer of the present invention.
FIG. 5 is a dyeing process route of the dyeing treatment of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides an epoxy modified hyperbranched polyamide-amine high molecular polymer, which comprises, by mass, 86 parts of methyl acrylate, 63-175 parts of diamine, 3-26 parts of dicyanodiamine and 1.5-26 parts of epichlorohydrin. The structural formula of the high molecular polymer is shown in fig. 4. Methyl acrylate and diamine are used as main raw materials, a Michael addition reaction and an amidation reaction are carried out to prepare hyperbranched polyamide-amine, dicyanodiamine is used for grafting amino and imino on branched chains of the hyperbranched polyamide-amine, and the branching degree of the polymer is further improved while the amine content of the hyperbranched polyamide-amine is controlled. Then reacting with epoxy chloropropane, introducing a reactive group epoxy group into a high polymer branched chain, and preparing the epoxy modified hyperbranched polyamide-amine high polymer.
In one embodiment of the present invention, the diamine comprises at least one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, and hexylenediamine.
The epoxy modified hyperbranched polyamide-amine high molecular polymer is prepared by the following method, and comprises the following steps:
s1, taking an organic solvent as a reaction medium, wherein the organic solvent can adopt methanol, adding methyl acrylate into a diamine solution in a dropwise adding mode, the mixed titration temperature is 10-25 ℃, after the mixed titration is finished, heating to 20-50 ℃, reacting for 12-48 h, and carrying out Michael addition reaction to generate an intermediate. The intermediate takes 50 ℃ as the initial temperature and 10 ℃ as the temperature gradient, the temperature is gradually increased to 120-150 ℃, the reaction is carried out for 2-4 h, and the amino and ester groups on other intermediates generate amidation reaction under the reduced pressure condition (the vacuum degree is 0.01-0.04 Mpa) at high temperature to carry out random growth, thereby preparing the hyperbranched polyamide-amine.
And S2, adding dicyandiamide into the reaction product of the S1, reacting for 2-4 h at the temperature of 80-85 ℃, wherein the added dicyandiamide is dicyandiamide aqueous solution, and adding dicyandiamide after dissolving dicyandiamide in water.
And S3, reducing the temperature of the system to 0-15 ℃, adding epoxy chloropropane, wherein the epoxy chloropropane is added in a dropwise manner, the titration temperature is maintained at 0-15 ℃, mixing, heating to 15-50 ℃, reacting for 0.5-2 h, and introducing reactive groups, namely epoxy groups, to the branched chain of the hyperbranched polyamide-amine.
The invention also provides application of the epoxy modified hyperbranched polyamide-amine high molecular polymer in modified cellulose fiber fabrics and a low-salt and low-alkali dyeing process of reactive dyes. The specific application mode is as follows: padding or dipping the cellulose fiber fabric with working solution, wherein the working solution is prepared from the epoxy modified hyperbranched polyamide-amine high molecular polymer product and water and has the concentration of 5-10 g/L, and then drying at 100-150 ℃. The cellulose fibers here can be cotton, viscose and hemp. The solid content of the epoxy modified hyperbranched polyamide-amine high molecular polymer adopted in padding or dipping is 20%.
Example one
The embodiment provides an epoxy modified hyperbranched polyamide-amine high molecular polymer, which is prepared by the following specific steps:
s1, weighing 111.19g of propane diamine at 20 ℃, dissolving the propane diamine in 50mL of anhydrous methanol, weighing 86.09g of methyl acrylate, dropwise and slowly dropping the methyl acrylate into a reaction system for about 2 hours, and rapidly stirring while dropping. After the completion of the dropwise addition, the reaction was carried out at 30 ℃ for 48 hours to obtain an intermediate product. Heating to 50 ℃, gradually heating to 140 ℃ by taking 10 ℃ as a heating gradient, reacting for 4 hours, collecting a distillation product methanol, and changing the product into a light yellow transparent viscous high polymer at the end point of the reaction.
S2, dissolving 4.2g of dicyanodiamide in 20g of water to form dicyanodiamide aqueous solution, adding the dicyanodiamide aqueous solution into the polymer obtained by the reaction of S1, and reacting for 4 hours at 85 ℃.
And S3, after the product is cooled, dropwise adding 4.63g of epoxy chloropropane into the reaction product of the S2 at 15 ℃, heating to 30 ℃ after titration, and carrying out heat preservation reaction for 2 hours. And after the reaction is finished, adding 100mL of water, and filtering to obtain the epoxy modified hyperbranched polyamide-amine high molecular polymer.
Example two
The difference between the present embodiment and the first embodiment is mainly as follows: in this example, 122.61g of pentamethylene diamine was used as diamine, the reaction temperature after completion of the titration of S1 was 40 ℃ and the reaction time was 24 hours, and the other reaction conditions and the amounts of the raw materials added were the same as those in example one.
EXAMPLE III
The difference between the present embodiment and the first embodiment is mainly as follows: in this example S1, 175g of hexamethylenediamine was used as diamine, 86g of methyl acrylate was added at 25 ℃ and reacted at 50 ℃ for 12 hours to obtain an intermediate product. The temperature is raised to 50 ℃,10 ℃ is used as a temperature raising gradient, the temperature is raised gradually to 150 ℃, the reaction time is 2h, and the equation of the reaction process is shown in figure 3. In S2, the addition amount of dicyandiamide is 26g, the reaction temperature is 85 ℃, and the reaction time is 2h. And the dropping amount of the epoxy chloropropane in the S3 is 26g, the dropping temperature is 10 ℃, and the reaction is carried out for 0.5h at the temperature of 50 ℃ after the dropping is finished.
Example four
The difference between the present embodiment and the first embodiment is mainly as follows: 63g of ethylenediamine was used as diamine in S1, the dropping amount of methyl acrylate was 86g, the dropping temperature was 10 ℃, and after completion of the dropping, the reaction was carried out at 20 ℃ for 48 hours, thus obtaining an intermediate product. The temperature is increased to 50 ℃, the temperature is gradually increased to 120 ℃ by taking 10 ℃ as the temperature gradient, and the reaction time is 3 hours. In S2, the addition amount of dicyandiamide is 3g, the reaction temperature is 80 ℃, and the reaction time is 3h. And (3) dripping the epoxy chloropropane at the temperature of 0 ℃ in an amount of 1.5g, and carrying out heat preservation reaction at the temperature of 15 ℃ for 2h after finishing dripping.
EXAMPLE five
The epoxy modified hyperbranched polyamide-amine high molecular polymer prepared in the first embodiment is prepared into a product with a solid content of 20%, the product is added with water to prepare a working solution with a concentration of 5g/L (the concentration is the concentration of the product, but not the concentration of the high molecular polymer), the pretreatment is carried out on pure cotton white cloth (provided by Zhejiang Yingfeng science and technology Co., ltd.) to carry out modification treatment, and the product is dried at 100-130 ℃ in a dipping-rolling manner to complete modification.
Example six
The present embodiment is different from the fifth embodiment mainly in that: this example uses the epoxy-modified hyperbranched polyamidoamine high molecular polymer prepared in example two.
EXAMPLE seven
The present embodiment is different from the fifth embodiment mainly in that: this example uses the epoxy modified hyperbranched polyamidoamine high molecular polymer prepared in example three.
Example eight
The present embodiment is different from the fifth embodiment mainly in that: this example uses the epoxy-modified hyperbranched polyamidoamine high molecular polymer prepared in example four.
Comparative example
The difference between the comparative example and the fifth example is mainly as follows: in the comparative example, the commercial cationic modifier product is adopted to modify the pure cotton white cloth, the solid content of the cationic modifier product is adjusted to 20%, the adjusted product is prepared into 5g/L working solution, and the modification process conditions are the same as those in the fifth example.
Dyeing process
The white cloth modified in the fifth to eighth examples and the comparative example was dyed, and the dyeing formula of the dye used in the dyeing process is shown in table 1 and the dyeing process route is shown in fig. 5, using the unmodified pure cotton white cloth as a blank control.
TABLE 1 dyeing recipe for five to eight examples, comparative examples and blank control
| Composition (I) | Blank group | Comparative example | EXAMPLE five | EXAMPLE six | EXAMPLE seven | Example eight |
| Amount of modifier (g/L) | / | 5 | 5 | 5 | 5 | 5 |
| Dye (owf/%) | 3 | 3 | 3 | 3 | 3 | 3 |
| Na 2 SO 4 (g/L) | 80 | 20 | 20 | 20 | 20 | 20 |
| Na 2 CO 3 (g/L) | 25 | 10 | 10 | 10 | 10 | 10 |
Dyed fabric detection
The dyed fabrics were examined by reference to the color fastness to rubbing of textile color fastness test (GB/T3920-2008) and the color fastness to soaping of textile color fastness test (GB/T3921-2008), and the dyeing conditions, color changes and color fastness of the reactive dyes were measured after dyeing cotton fabrics, and the results are shown in Table 2.
TABLE 2 results of dyeability and color fastness measurements of various groups of dyed fabrics after dyeing treatment
As can be seen from table 2, the epoxy modified hyperbranched polyamidoamine high molecular polymer prepared in each example of the present invention is used to modify the fabric, and the modified fabric is used in the low-salt and low-alkali process of reactive dye, and the color depth value (integer value) of the dyed fabric is similar to that of the dyed fabric of the comparative example. However, compared with the unmodified dyed fabric, the fabric apparent color yield, namely the color depth value/Integ value, of the modified fiber used in the low-salt low-alkali dyeing process is obviously improved, the color light change is small, and the improvement of the quality control of the dyed finished product is facilitated. Meanwhile, the integral color fastness performance of the dyed fabric modified by the embodiments of the invention is excellent, and the modification of the high molecular polymer improves the comprehensive performance of the dyed fabric, so that the dyed fabric has good market application prospect.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The epoxy modified hyperbranched polyamide-amine high molecular polymer is characterized in that: the raw materials comprise, by mass, 86 parts of methyl acrylate, 63-175 parts of diamine, 3-26 parts of dicyanodiamine and 1.5-26 parts of epichlorohydrin.
2. The epoxy-modified hyperbranched polyamidoamine high molecular polymer of claim 1, wherein: the diamine comprises at least one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine and hexylenediamine.
3. A process for preparing the epoxy-modified hyperbranched polyamidoamine high molecular polymer according to claim 1 or 2, characterized in that: the method comprises the following steps:
s1, adding methyl acrylate into diamine by taking an organic solvent as a reaction medium, mixing at the temperature of 10-25 ℃, heating to 20-50 ℃ after mixing, reacting for 12-48 h, continuously and gradiently heating to 120-150 ℃, and reacting for 2-4 h;
s2, adding dicyanodiamine into the reaction product of the S1, and reacting for 2-4 h at the temperature of 80-85 ℃;
s3, reducing the temperature of the system to 0-15 ℃, adding epoxy chloropropane, mixing, heating to 15-50 ℃ and reacting for 0.5-2 h.
4. The production method according to claim 3, characterized in that: the organic solvent is methanol.
5. The production method according to claim 3, characterized in that: the temperature rise gradient of the gradient temperature rise is 10 ℃.
6. The production method according to claim 3, characterized in that: and the dicyandiamide added in the S2 is dicyandiamide aqueous solution.
7. The use of the epoxy-modified hyperbranched polyamidoamine high-molecular polymer according to claim 1 or 2 in modified cellulosic fiber fabrics and in low-salt and low-alkali dyeing process of reactive dyes.
8. Use according to claim 7, characterized in that: and (2) padding or dipping the cellulose fiber fabric in working solution and then drying, wherein the working solution is prepared from the epoxy modified hyperbranched polyamide-amine high polymer product and water and has the concentration of 5-10 g/L.
9. Use according to claim 8, characterized in that: the solid content of the epoxy modified hyperbranched polyamide-amine high polymer is 20%.
10. Use according to claim 7, characterized in that: the cellulose fibers include cotton fabrics, viscose fabrics and hemp fabrics.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116376013A (en) * | 2023-06-05 | 2023-07-04 | 四川省纺织科学研究院有限公司 | Preparation method and application of guanidine salt modified hyperbranched polyamide-amine composite fixation polymer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4718918A (en) * | 1984-01-03 | 1988-01-12 | Sandoz Ltd. | Treatment of textile materials to improve the fastness of dyeings made thereon and polymers useful therefor |
| DE19905877A1 (en) * | 1999-02-12 | 2000-08-17 | Daimler Chrysler Ag | High strength polymer resin |
| CN101070676A (en) * | 2007-05-18 | 2007-11-14 | 广东德美精细化工股份有限公司 | Fiber-material modifying method and dyeing process |
| CN101413216A (en) * | 2008-11-26 | 2009-04-22 | 山东金鲁化工有限公司 | Cellulose fiber modifier |
| CN110204710A (en) * | 2019-06-04 | 2019-09-06 | 浙江九沐兰科技有限公司 | A kind of preparation method and application of the dendroid polyamines cationoid modifying agent of dynamics model |
-
2022
- 2022-12-30 CN CN202211738187.6A patent/CN115894911B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4718918A (en) * | 1984-01-03 | 1988-01-12 | Sandoz Ltd. | Treatment of textile materials to improve the fastness of dyeings made thereon and polymers useful therefor |
| DE19905877A1 (en) * | 1999-02-12 | 2000-08-17 | Daimler Chrysler Ag | High strength polymer resin |
| CN101070676A (en) * | 2007-05-18 | 2007-11-14 | 广东德美精细化工股份有限公司 | Fiber-material modifying method and dyeing process |
| CN101413216A (en) * | 2008-11-26 | 2009-04-22 | 山东金鲁化工有限公司 | Cellulose fiber modifier |
| CN110204710A (en) * | 2019-06-04 | 2019-09-06 | 浙江九沐兰科技有限公司 | A kind of preparation method and application of the dendroid polyamines cationoid modifying agent of dynamics model |
Non-Patent Citations (1)
| Title |
|---|
| 王国建: "《高分子现代合成方法与技术》", vol. 1, 同济大学出版社, pages: 95 - 96 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116376013A (en) * | 2023-06-05 | 2023-07-04 | 四川省纺织科学研究院有限公司 | Preparation method and application of guanidine salt modified hyperbranched polyamide-amine composite fixation polymer |
| CN116376013B (en) * | 2023-06-05 | 2023-11-24 | 四川省纺织科学研究院有限公司 | Preparation method and application of guanidine salt modified hyperbranched polyamide-amine composite fixation polymer |
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